Polyisocyanurate biuret surfactants

ABSTRACT

A MIXTURE OF MOLECULES CONTAINING ALL OF THE FOLLOWING GROUPS SHOW EMULSIFYING ABILITY: ISOCYANURATE, METAL ISOCYANURATE AND BIURET.

Oct. 16, 1973 P A. ARGABR|GHT ET A1. 3,766,086

POLYISOCYANURATE-BIURET SURFACTAN'TS Filed June 28, 1971 2 Sheets-Sheet`1 Fig. 2

@,CRCC C@ COZCHS C02H s-c2H5 SH C 0H o c v 9 9 9 i 9 O @@@V @El Q@ CO CH2 3 PERRY A. ARGABRIGHT CH C. TRAVIS PRESLEY 2 Q CHARLES B. WENGER HlCHS cZHS

Hl CH CH3 CH3 CH 2 v A T TOR/VFY Oct. 16, 1973 P. A. ARGABRIGHT E'rAL3,766,086

POLYISOCYANURATEB I URET SURFACTANTS Filed June 28, 197,1 2 Sheets-SneetcYcLoHEPTATRn-:NE

@ @@,Q Q' Q w @,QQmf

( s: SATURATED 1 CH3 CH3 ARALKYL: '7 cH -c c- -cH cH- ARYLARALKYL No2cHa- -cH2 cHz- Q( CH2);

ALKENE CH2- H WHERE n MAY BE FROM l o 50) BICYCLIC /NVENTORS PERRY A.ARGABRIGHT C. TRAVIS PRESLEY CHARLES B. WENGER A TTORN United StatesPatent Office 3,766,086 Patented Oct. 16, 1973 U.S. Cl. 252-312 7 ClaimsABSTRACT F THE DISCLOSURE A mixture of molecules containing all of thefol-lowing groups show emulsifying ability: isocyanurate, metallsocyanurate and biuret.

CROSS-REFERENCES TO RELATED APPLICATION S The following U.S. patentapplications relate to compounds and uses which are generally related tothe present invention: Ser. No. 224,905, led Feb. 9, 1972; Ser. No.224,904, filed Feb. 9, 1972; Ser. No. 715,199, filed Mar. 28, 1968; Ser.No. 89,883, filed Nov. 16, 1970; Ser. No. 72,388, led Sept. 15, 1970;Ser. No. 72,288, tiled Sept. 15, 1970.

BACKGROUND OF THE INVENTION Field of the invention The present inventionrelates generally :to the eld of isocyanurate-containing organiccompounds generally classified within Class 260, subclasses -248 and88.3 of the United States Patent Office.

Description of the prior art The present invention is concerned with anew class of emulsifying agents. The prior tart which might begenen-ally relevant is U.S. 3,072,654 which teaches calciumdi(dichloroisocy=anurate) in Ibleaching and cleaning compositions at itsco1. 1, lines 9 32; US. 3,272,813 which complexes chloroisocyanurateswith potassium to make bleaching compositions at its col. 16, lines63-70; U.S. 3,489,696 which forms polyarnides from isocyanurates andpolycarboxylic acids .and mentions use of biuret triisosyanate at col.5, line 62; on the basic hydrolysis of disubstituted isocyanurates,Argabright and Phillips, Journal of Heterocyclic Chemistry, 7, 999(1970) which teaches formation of relatively simple biurets. Pn'or artof lesser interest includes U.S. 3,150,132, U.S. 3,251,818, U.S1.3,252,942, U.S. 3,275,630. None of the aforementioned prior fart teachesthe compounds of the present invention or in any way discloses their useas surfactants.

SUMMARY OF THE INVENTION General Statement of the invention The presentinvention relates to a new class of compounds which `are useful asemulsifying agents, e.g., .in forming dspersions and emulsions. Thesecompounds are characterized by containing in :a single molecule all ofthe following groups:

metal lsoeyanurate I I The compounds of the present invention have th-egeneral structure shown in FIG. 1;

where:

R=divalent hydrocarbon or substituted hydrocarbon radical, as describedbelow land exemplified in FIG. 2.

X=a metal, or hydrogen or quaternary ammonium (which, for the purposesof this invention, acts like a metal) or a 'combination thereof.Particularly preferred are hydrogen, quaternary ammonium and metalsselected from the following groups of the Periodic Table; Ia, Ib, Ha,IIb, IIIa, IIIb, IVa, IVb, Va, Vb, Vla; including such meals as Li, Na,K, Rb, Cs, Ca, Ag, Au, Be, Mg, Ca, Sr, Ba, Ra, Zn, Cd, Hg, B, Al, Sc, Y,La, land the other rare earths, Ac, Ga, In, T1, Ti, Zr, Hf, Ge, Sn, Pb,V, Nb, Ta, Sb, Bi, Cr, Mo, W, Mn, Fe, Ru, Co, Ni, Rh, Pd, Os, and Ir.

A=a monovalent organic radical selected from the following: isocyanateurethane (NHCO'2R), urea (--NHCONHR'), amino (-NH2), NHR' or NR2)R=monova1ent hydrocarbon or substituted hydrocarbon radical, asdiscussed below;

m-a=averfage number of trisubstituted isocyanurate rings and is apositive integer from 0 to about 400, and most preferably from 0 toabout 200.

n-b=average number of isocyanuric acid and/or isotcyanurate salt groups'and is a positive integer from 1 to about 10,000, more preferably from2 to about 1000, and most preferably from 3 to about 100.

a=average number of trisubstituted biuret groups, as

described below, and is a positive integer from 0 tov about 2000, morepreferably from 0 to about 400', and most preferably from 1 to about200.

b==average number of disubstituted biuret groups, as described below,and is a positive integer lfrom 1 to 'about 9000, more preferably from 2to about 5000 and most preferably from 3 to about 1000.

2m+n+1=average number of divalent R groups and is a positive integerfrom 2 to about 11,000, more preferably from 3 to about 1,100 and mostpreferably from 4 to about 140.

m|2=average number of A groups and is a positive integer from 2 to about2000, more preferably from 2 to about 400 and most preferably from 2 toabout 200;

bonds and no A-to-A bonds and no R-to-R bonds.

R preferably contains 2 to 40, more preferably 2 to 30, and mostpreferably 2 to 18 carbon atoms.

R preferably contains 1 to 40 carbon atoms, more preferably 1 to 20carbon atoms and most preferably 1 to 10 carbons, for example -CH3,-C2H5, -C3H7, i-C3H7,

s ES, @1 -01120112011, CHa-b-cHz-,

CH3 CH2=CH-CHZ, @-01% ctc.

etc. where R may be hydrogen, lower alkyl (e.g., ethyl, hexyl) or aryl(e.g. monovalent radicals corresponding to the aryl radicals describedin FIG. 2. The examples of R (shown in FIG. 2) are set forth forpurposes of elucidation, not restriction.

It will be recognized that the values of m and n described above are onthe basis of the integers which will be used to describe a singlemolecule. In actual practice, the invention will involve mixtures ofmolecules of the general form described above. Thus, the average valueof m-a for the mixture may be from about 1 to about 2000, morepreferably from about 1 to 400, and most preferably from about 1 to 200;the average value of n-b may be from about 0.5 to 10,000, morepreferably from about 0.5 to 1000, and most preferably from about 0.5 to100; the value of a may be from about 0 to 2000, more preferably from to400, and most preferably from 2 to 200.

The present invention relates to a new class of emulsifying agents,their preparation, and processes for their use. For example, thecompounds of the present invention may be added to immiscible mixturesof water and organic compounds, e.g., equal parts by volume of water anda hydrocarbon and the resulting mixture agitated to form emulsions. Thisresult is all the more surprising as many of the compounds are only veryslightly soluble, and some are insoluble, in either phase.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows the general formula ofthe products of the present invention.

FIGS. 2 and 3 exemplify some of the possible structures of R groups ofthe starting materials and products of the present invention.

FIG. 4 shows the general formula of the organic starting materials ofthe present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Starting materials The startingmaterials for the present invention are salts of polyisocyanuric acidsproduced according to the techniques taught in copending U.S. patentapplication S.N. 715,199, led Mar. 22, 1968, now U.S. Pat. 3,573,- 259,by reacting a metal cyanate and an organic diisocyanate in the presenceof an aprotic solvent to form isocyanurate-containing polyisocyanatemetal salts.

It has been discovered that aqueous solutions of the aforementionedpolyisocyanurate salts, of the general formula shown in FIG. 4 (wherethe lettered groups are as described above under Summary of theInvention), under basic conditions (i.e., pH in excess of 7) gives thebiuret product shown in FIG. 1. The product is dramatcally less solublein water than is the polyisocyanurate salt reactant. Suitable basesinclude alkali metal or alkaline earth metal hydroxide.

Reaction media- Water or mixtures of water and an alcohol, ketone,ester, amide, sulfoxide, sulfone, etc.

Temperature-While not narrowly critical, temperatures in the range from10 to about 200 C. are preferred, with 15-150 C. being more preferredand 20-120 C. being most preferred. The lower limit is generally thefreezing point of solution and the upper limit is generally the boilingpoint of the solution at the reaction pressure.

Pressure-While not narrowly critical, the reaction can be carried out atpressures of from 0.5 t0 100, with 0.6 to 50 being more preferred, and0.7 to 10 atmospheres being most preferred.

T ime.-The reaction time, of course, is dependent on the initialconcentration of the starting materials and the temperature. Thepreferred time is from 0.01 to 4500 hours, more preferred 0.05 to 350hours, and most preferred from 0.06 t0 200 hours.

Examples:

EXAMPLE I Preparation of polyisocyanurate salt To a stirred slurry of82.4 KOCN (1.02 mole) in 2000 ml. of dimethylformamide (DMF) at 75 C.,183 g. of tolylene diisocyanate (1.05 mole) is added at a rate of 0.85ml./min. by means of a syringe pump.

The entire operation is carried out in a nitrogen atmosphere. Followingthe addition, the reaction mixture is stirred an additional 5 minutes,dry methanol added (large excess) and allowed to react for an additionalhour to insure complete quenching. The major product is insoluble in DMFand thus readily separated by a single filtration. A trace DMF solubleproduct is obtained after solvent stripping the filtrate. After vacuumdrying at C. to remove residual DMF and methanol, the following yieldand analytical data are obtained:

Aryl/end Average Percent group 2 ratio in ol. wt.

Product yield l (2m-|-n+1/m+2) (minimum) DMF insoluble a 96. 5 21. 2 10,000 DMF soluble Trace 1.5 750 1 Corrected for residual DMF. 2 Measuredby nuclear magnetic resonance spectroscopy. l Contains 20.9% DMF ofsalvation.

EXAMPLE II Preparation of polyisocyanurate biuret EXAMPLE III Theutility of the polyisocyanurate biuret as an emulsifying agent isdemonstrated in the following manner.

To a graduate, containing 10 ml. of n-heptane and 9 ml. of water(deionized and distilled) is added 2 ml. of the crude suspension ofExample II. Subsequent shaking provides a stable emulsion having avolume of approximately 16 ml.

EXAMPLE IV In a manner similar to Example III, 10 ml. of n-heptane, 10ml. of water and 0.5 ml. of the suspension prepared in Example II onshaking, gives approximately l1 ml. of emulsion, which remains stable.

Modifications of the invention It should be understood that theinvention is capable of a variety of modifications and variations whichwill 3,766,086 5 6 be made apparent to those skilled in the art by areading of the specification and which are to be included within OiJLCHs CHIOH NH2 C/ 0H the spirit of the claims appended hereto.

What is claimed is: 1. A composition comprising a mixture of compounds 5containing in a single molecular isocyanurate, metal isocyanurate andbiuret groups, and having the structure:

i l I 0 N ll L N N t V0 ro =V W20 O-r/Nr-O R- m n A m N N N- I /N- ILIL- 12++1 ]+z NH o \N m-a n-b b wherein o 0 R=divalent hydrocarbon orsubstituted hydrocarbon H N CHa H N g CHa SoaH SOaCHa 0, g CE radical,containing 2 to about 40 carbon atoms, l l X is selected from the groupconsisting of metals, hy-

drogen, or quaternary ammonium radicals, l l A is a monovalent organicradical selected from the group consisting of -NHCO2R, -NHCONHR',

-NH2, -NHR and -NRZQ wherein R' is a monovalent hydrocarbon radical orsubstituted 25 hydrocarbon radical containing from 1 to about 40 NHNH20=CCHx ou@ 5N Ifof carbon atoms, wherein I m-a is the average number oftrisubstituted isocyanurate rings per molecule and is a positive integerfrom zero to about 400, 3

n-b is the average number of isocyanurate acid and/0r isocyanurate saltgroups and is a positive integer from 1 to about 10,000, wherein l l ais the average number of trisubstituted biuret groups,

and is from about 0 to about 2,000, wherein 35 b is the average numberof disubstituted biuret groups and is from about 1 to about 9000,2m+n+l=the average number of divalent R groups and is a positive integerfrom 2 to about 11,000, and

mei-2 is the average number of A groups and is a positive integer from 2to about 2,000, and wherein there are no N-to-N bonds and no A-to-Nbonds, and no A-to-A bonds and no Rto-R bonds. 2. A process according toclaim 1 wherein R is selected 45 CHP@ from the group of organic radicalsconsisting of:

CH3 CH l 002cm 02011 Hr I I CH: @f (Where nr=F, o1, Br or I),

l O no s' PoaH 002cm ooZH s-ozm SH COZCHH i CH3 CH3 CH3 .@6@

3. Compositions according to claim 1 wherein X is selected from thegroup consisting of hydrogen, quaternary ammonium radicals and metalradicals selected from the following groups of the Periodic Table; Ia,Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vla.

4. Compositions according to claim 1 wherein m-a is a positive integerfrom to about 200, wherein n-b is a positive integer from 3 to about100, wherein a is a positive integer from 1 to about 200, and wherein bis a positive integer from 3 to about 1,000, and wherein 2m|n|l is apositive integer from 4 to about 140, and wherein m-i-Z is a positiveinteger from about 2 to about 200.

5. Compositions according to claim 1 wherein R is selected from thegroup of organic radicals as shown below:

CHT-CHu-(i H CH2-C Hz-CHI CaH1 CHQ- C H-CHz-CH;

S'OaCH;

s l Y S CH3 S v s v c1-Ir con 1x11 CH,

(lo Ch CH3 CH, @6116@ and the substitute derivatives thereof which aresubstituted with radicals selected from the group consisting of NO, Cl,F, Br, I, CN, -CO2R', -CO-R, -O-R, -SR,

9 10 naphthyl, alkyl (1-40 carbon atoms), POaR, cyclohexyl, 7. Anemulsion comprising both Water and at least one cyclopropyl,-polymethylene -OCOR, compound according to claim 1.

1li References Cited NC0R" 5 UNITED STATES PATENTS where R may behydrogen, lower alkyl or aryl. 3,573,259 3/ 1971 Agabfight et al-260-77-5 NC 6. A composition according to claim 1 wherein R' con- OTHERREFERENCES tains from 1 to 10 carbon atoms and is selected from thegroup consisting of Noller: Chemistry of Organic Compounds, W. B. Saun-10 ders Co., Philadelphia, 1951, p. 186. om -CzHs -CaHL i-CsHv, S DONALDE. CZAJA, Primary Examiner M. I. WELSH, Assistant Examiner s 15 Us. C1.XR.

CHZCHZoiL cHa-rlz-CHH CH1=oH-cH-, Uw

Ha 252-356, 357; 260-29.2, TN, 77.5 NC, 248 NS.

Page l of 2 UNITED STATES PATENT OFFICE `CERrIIlFICAJIE 0F -CORRECTIONPatent No. 3,766,086 Dated @ctooer 16, 1975 nventof) Perry A.i-rffahrifrht et al.

It is certified that error appears n the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 5, structures of Claim l should read as follows:

olumn 5, lines 4 6 through 65 lshould read as follows:

c can, cHBcH-cn-CH3 CH2-wen cucmcr cuzcHZ-c'H-cmcnz 'eeeioa (WHERE HIF,C|,Br or I) UNITED STATES PATENT 2. CERTIFICATE OF CORRECTION It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as show-n below:

Column 7, line 17 Following Va, add Vb Column 7, lines 30through 55should read as follows:

lCH3 63H7 CH3-CH-CH2-CH3 CH2CHC\H CHCH=CI i2 CH2CH2-CH2CH=CH2 cH @e e@e@ i PO3H cogen3 (WHERE HI F,Cl, Br orI) a y ,Signed and Sealed thisThirteenth D ay 0f September 1977 [SEAL] A ttest:

RUTH C. MASON LUTRELLE F. PARKER Attesting Officer Acting Commissionerof Patents and Trademarks

